Abstract: H-1 and C-13 NMR studies and quantum chemical calculations show the interaction between 2,11-dithia-5,6,8,9-tetramethyl[3(2)](1,4)cyclophane and nitrosonium cation to result in the formation of - and n-complexes. According to DFT/B3LYP/6-31G(2d,p) calculations, formation of nitrosonium complexes is a strongly exothermic process both in gas phase and in SO2. Affinity of single-charged complexes to NO+ is usually larger than that of double-charged and triple-charged complexes, affinity of all the charged complexes to nitrosonium cation in SO2 being larger than that in gas phase. The -complex with nitrosonium cation coordinated to the methylated aromatic ring is the most stable with structural characteristics being close to those obtained by X-ray diffraction for nitrosonium -complexes of hexamethylbenzene and other arenes. The N?O bond lengths in all the complexes are quite close to each other and larger than that in NO+ cation. The S?N bond length increases upon transition from single-charged to double-charged and polycharged complexes. Copyright (c) 2014 John Wiley & Sons, Ltd.

Cite: Borodkin G.I. , Elanov I.R. , Andreev R.V. , Shakirov M.M. , Shubin V.G.
Nitrosonium complexes of 2,11-dithia-5,6,8,9-tetramethyl[3(2)](1,4)cyclophane: a combined experimental and theoretical study
Journal of Physical Organic Chemistry. 2014. V.27. N6. P.470-477. DOI: 10.1002/poc.3284 WOS Scopus РИНЦ

Dates:

Published online:	Feb 5, 2014
Published print:	Jun 1, 2014

Identifiers:

Web of science	WOS:000336501400002
Scopus	2-s2.0-84900468632
Elibrary	21877634
OpenAlex	W2538095203

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